Azo dye



invention.

Patented Mar. 16, 1943 AZO DYE Joseph B. Dickey and James G. McNaily, Rochester, N. Y., alsignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No ni-awin'r.

Application September 19, 1939, Serial No. 295.648

2 Claims. (Cl. 260-193) This invention relates to new azo compounds and their application to the art or dyeing or coloring.

We have discovered that the azo compounds having the general formula:

wherein R represents the residue of a member selected from the group consisting of an aryl coupling component of the benzene series, an aryl coupling component of the naphthalene series, a heterocyclic coupling component and an acetoacetarylamide coupling component and in which said aryl coupling components are Joined to the 9.20 bond shown through a nuclear carbon atom constitute a valuable class of compounds. Depending upon their structure, the azo com- It is an object or our invention to provide a new class or azo compounds. Another object of our invention is to provide dyed textile materials pounds of our invention possess application for the dyeing or coloration of organic derivatives of cellulose, wool, silk, viscose and wallpaper.

Both sulfonated and non-sulfonated compounds are included within the scope of our The nuclear non-sulfonated compounds, other than those in which the coupling component is an acetoacetarylamide, are particularly of value for the dyeing of organic derivatives of cellulose although they possess some application tor the dyeing or wool and silk. For the dyeing 01 organic derivatives of cellulose, the nuclear non-sulfonated compounds, wherein R is the residue 01 an aryl coupling component of the benzene series, are generally advantageous. This is particularly so when R contains an N-alkyl group in para position to the azo bond. Preterably when the dye compounds of our invention .are to be employed for the dyeing of organic derivatives of cellulose, they should contain no nuclear free carboxylic acid group.

the dye compounds of our which are of good Iastness to light and washing.

,Another object of our invention is to provide a process for the dyeing or coloration of organic derivatives of cellulose, wool, silk, viscose and wallpaper. A still further object or our invention is to provide a new class of nuclear nonsulfonated azo dye compounds suitable for the dyeing or colorationot cellulose acetate silk textile materials. Other objects will hereinafter appear.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate or cellulose butyrate and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellu-' lose such as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such as methyl cellulose, ethyl cellulose or benzyl cellulose. While our inventoin will be illustrated more particuarly in connection with the coloration of cellulose acetatesilk, a material to which the, invention is especially adapted, it will be understood that it applies to the coloration of other organic derivatives oi cellulose, such as those Just named, as well as to the coloration or wool, silk, viscose and wallpaper.

The azo dye compounds of our invention can be prepared by diazotizing 1-amino-2,4-dinitro- G-hydroxybenzene and coupling the diazonium compound obtained with an aryl coupling comheterocyclic coupling component or an acetoacetarylainide couphng component. As previously' indicated, when an aryl coupling compopent of the benzene or naphthalene series is employed, said coupling component is joined to the,

8.20 bond through a nuclear carbon atom.

it will be understood that alkyl as used herein, unless otherwise indicated, includes not only unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group or a butyl group but also substituted alkyl groups such as ,s-hyciroxyethyl, firy-hydroxypropyl, p-hydroxypropyl,

p-methoxyethyl or p-ethoxyethyl, for example.

The following examples illustrate the prepara tion of the azo compounds of our invention:

Exzmrta 1 A. 20 grams of 1-aniino-2,4-dinitro-6-hydroxybenzene are dissolved in 225 cc. oi. hot glacial acetic acid and the resulting solution is then cooled rapidly" to room temperature.

B. 7.6 grams otsodium nitrite are dissolved in 55 grams of 100% sulfuric acid at 15 C. and the resulting solution is warmed to 70 C. following which it is cooled to l5-20 C.

The mixture prepared in B is added to the mixture prepared in A over a period 01 30.45 minutes while stirring and maintaining a tem'-' perature of 15-20" C.- Stirring is continued at room temperature for several hours and then 1 gram of urea is added to remove any excess nitrous acid.

12.8 parts of barbituric acid are dissolved in 200 parts of water to which has been added 81 parts of sodium carbonate and the resulting solution is cooled to a temperature approximating 0-10 C. by the addition of ice, for example. The diazo solution prepared as described above is then added with stirring and concurrently I with its addition an aqueous solution oi! sodium acid and the dye compound formed is recovered by filtration, washed with water and dried. The

dye compound obtained colors cellulose acetate silk, wool and silk a greenish-yellow color.

Similarly, by the substitution of an equivalent gram molecular weight of acetoacetanilide, o-

chloroacetoacetanilide and p-p-hydroxyethoxyacetoacetanilide for the barbituric acid of the above example, pigment dyes included within the scope of our invention can be obtained.

EXAMPLE 2 18.1 grams of di-p-hydroxyethylaniline are dissolved in glacial acetic acid and the resulting solution is cooled to a temperature approximating 0-10 C. The diazo solution prepared as described in Example 1 is then added with stirring, while maintaining a temperature: 01 15 0-10 C. Upon complete addition of the diazo solution, the mixture is permitted to stand for awhile after which it is made neutral to Congo 1 2,a1s,7ss

red-paper by the addition of sodium acetate.

Water is then added to the mixture and the precipitated dye compound formed is recovered by filtration, washed with water and dried. The dye compound obtained colors cellulose acetate silk a rubine shade.

Exsuru: 3

29 grams of butyl sodium-'e-sulfoethyl-mtoluidine are dissolved in glacial acetic acid and coupled with 20 grams of diazotized l-amino- 2,4-dinitro-6-hydroxybenzene. Coupling and recovery of the dye compound may be carried out as described in Example 2. The dye compound obtained colors celluloseacetate silk a violet shade.

' Exams: 4

.1 gram mole of son, 1 1 223B. 8 N u HOHCHzOH is dissolved in glacial acetic acid and the resulting solution is cooled to a. temperature approximating 0-10" C. The diazo solution prepared as described in Example 1 is then added ,with stirring while maintaining a temperature of 0.l0 C. The coupling reaction which takes place is completed by adding sodium carbonate until the mixture is neutral to Congo red paper. The dye compound formed is recovered by filtration, washed with water and dried. The dye compound obtained colors cellulose acetate silk 9. blue shade.

The following tabulations further illustrate the compounds included within the scope of our invention. The compounds indicated below may be prepared by diazotizing the amines listed under the heading Amine" and coupling the diazonium compounds obtained with the compounds specified in the column entitled "Coupling component. The diazotization-and coupling reactions may, for example, be carried out following the general procedure described in Examples 1 to 4, inclusive.

Table A.

Color on cellulose Amino Coupling component acetate silk, wool andsilk .1-amino-2,4-dinitro-0-hydroxybenzene... 2,4-dlhydroxyquinn' Greenisli-yellow.

D 2,4-dlhydroxypyri ln Do.

ggpng g g eny me y- Dyrazo one ran ae ow. O-K/Ietlwxyaoetoaoetanill e.. YelloEw. 1 fi inr lmtoluidin Pu 1 -1- V 0m 0we. G] oerylcresidino 150. Et yl glyceryl oresidine Violet. Ethyl-y-chloro-fl-gf droxy-propyl cresldine Do. Amylsodlum B-s iatoethyl-eresidine. Do. fl-Hydroxypropyiauiline-.. Rubine D Ethylanillne Do.

Do Dlethylanlline Violet.

Do Ethyl-fl-hydroxyethyl-2 5-dimethoxyaniline. Vloletur 1e.

Do Glyceryl-2,li-diethox an e Reddis -b uo.

D Glycoryl-a-nsphthy amine Blue.

1) flHydroxyeth l-a-nephthylamine D0.

Glyoeryl buty -m-toluidine 1e. 1-methoxy-2-ethylglyceryl-amino-i-acetaminobenzene Blue-green.

. 6 Do 6 Blue.

N om

2,318,738 3 Table A-Continued 1 Color on cellulose Amine Coupling component acetate silk, wool and silk 1-amine-2,4-dinitro-6-hydroxybonzone.- G1yceryl-iM-dimethyl-bemomorpholene Blue.

Do Glyoeryl-7-aoetamino-benzomorpliolene Do. Glgoeryl-o-acotamino-benwmorpholene Do. Et yl-b-etbylbenzomorpholeno Do. fi-Hydroxyethyl-b-ohloro-benzomo holene Do. Glycoryl-7-mothyltetrahydroquino 6.. Do. Ethyl-B-metbyltetmh droquinolineuui Do. Tetraliydroquinollne nzotetronioacid. Greenish-yellow. Di-fi-hydroxyethyl-m-cblor e ed. m-Tcluidine yl cresidine h i-B-hydroxycthylam o-o-napht ol -Hydroxypropylaniline Rub Glyoeryl-'aoetamino-tetrahydroquinolino.. Blue.

s y roxye yy :0: rs roq o e o. l-lrninobarbiturio Mid y Yellow. Thiobarbiturlo acid Do. Z-imino-ll-oyanobarblturio acid Do. i-methylthiobarbiturio acid D0.

Table B Amine Coupling component Golgi; (an vriglgefllk,

i-amino-2,i-dinitro-fi-hydroxybenzene.. 2-naplitlioi-5-sulionic acid Red.

D l-amino-b-nafihthol-B-sulionio acid Blue-green.

l-suliopheny -3-methyl-5-pyrazolone Greenish-yellow.

It will be understood that the specific dye compounds given hereinbefore are intended to be illustrative and not limitative of the invention. Any of the amines disclosed herein may be diazotized and the diazonium compounds obtained coupled with any of the coupling components shown herein to obtain dye compounds included within the scope of our invention.

In order that our invention may be clearly understood, it is here noted that 1-amino-2,4-dinitro-fi-hydroxybenzene can be prepared as described in the Journal of the Chemical Society, page 2345 (1931), part II.

Both water soluble and water insoluble azo dye compounds are included within the scope of our invention. Those compounds, other than those in which the coupling component is an acetoacetarylamide, which are insoluble in water, may be advantageously employed for the direct dyeing of textile materials by grinding the dye to a fine powder, intimately mixing it with a suitable dispersing or solubilizing agent and adding the resulting mixture to water or a dilute solution of soap in water to form an aqueous dyebath. Following this known preparation of the dyebath;

the textile material or materials to be dyed may be added to the dyebath and the dyeing operation conducted in known fashion. For a more complete description as to how these water insoluble azo dye compounds of our invention can be employed for the dyeing of organic derivatives of cellulose, reference may be had to our United States Letters Patent No. 2,115,030, issued April 26, 1938. These water insoluble azo dye compounds of our invention as previously noted also possess application for the dyeing or wool and silk and they may be applied to these materials in the same manner as they are applied to organic derivatives of cellulose.

The water soluble dye compounds of our invention, other than those in which the coupling component is an acetoacetarylamide, may be applied to wool, silk, cotton, regenerated cellulose and (depending upon the nature and position of the water solubilizing group) organic derivatives of cellulose textile materials from an aqueous solution of the dye which may contain-salt. These water soluble dye compounds can be applied to the fiber in substantially the same manner as the water insoluble dye compounds. In the case of the water soluble dye compounds. however, the use of a dispersing or solubilizing agent is not necessary. It will be understood, of course, that the above remarks concerning the application of the dye compounds of our inwherein R represents the residue of an acetoacetarylamide coupling component.

2. The azo dye compounds having the general formula:

wherein R1 represents the residue of an aryl "nucleus of the benzene series containing .but one benzene ring. v

JAMES G. McNALLY. JOSEPH B. DICKEY. 

